In situ current collector

ABSTRACT

Electrochemical cells comprising electrodes comprising lithium (e.g., in the form of a solid solution with non-lithium metals), from which in situ current collectors may be formed, are generally described.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/002,097, filed Jun. 7, 2018 and entitled “In Situ Current Collector,”which claims priority to U.S. Provisional Application No. 62/517,409,filed Jun. 9, 2017 and entitled “In Situ Current Collector,” each ofwhich is incorporated herein by reference in its entirety for allpurposes.

TECHNICAL FIELD

Electrochemical cells and methods of forming and using the same aregenerally described.

BACKGROUND

Electrochemical cells typically include a cathode comprising a cathodeactive material and an anode comprising an anode active material. Thecathode active material and the anode active material can participate inone or more electrochemical reactions, which can be used to generateelectrical current.

The anode and the cathode of the electrochemical cell typically includecurrent collectors, which are used to transport electrons into and/orout of the electrode with which the current collector is associated.Most typically, the current collector is in the form of a metal layeradjacent to the region in which the electrode active material islocated. One disadvantage of using a metal sheet is its poor adhesion tothe electrode and therefore reduced electrical contact between thesetwo.

Accordingly, improvements to electrochemical cells are desired.

SUMMARY

Electrochemical cells comprising electrodes comprising lithium, fromwhich in situ current collectors may be formed, are generally described.The subject matter of the present invention involves, in some cases,interrelated products, alternative solutions to a particular problem,and/or a plurality of different uses of one or more systems and/orarticles.

In one aspect, an electrochemical cell is described. The electrochemicalcell may comprise a cathode. The electrochemical cell may furthercomprise an anode comprising a solid solution of lithium and at leastone non-lithium metal, the anode having an active surface. Theelectrochemical cell may further comprise an electrolyte inelectrochemical communication with the cathode and the anode. Theelectrochemical cell may be configured such that it is in a chargedstate when it is first assembled. The electrochemical cell may be underan applied anisotropic force having a force component normal to theactive surface of the anode.

In some embodiments, the anisotropic force and the electrochemical cellmay be configured such that, when the electrochemical cell is fullycycled 10 times, the anode has a porosity of less than 20% immediatelyafter the discharge of the tenth cycle, and 75 wt % or less of theamount of lithium present in the anode in its initial fully-chargedstate remains in the anode immediately after the discharge of the tenthcycle.

In some embodiments, the at least one non-lithium metal may be presentat a sufficient volume such that, when the electrochemical cell is fullycycled 10 times, the anode has a porosity of less than 20% immediatelyafter the discharge of the tenth cycle, and 75 wt % or less of theamount of lithium present in the anode in its initial fully-chargedstate remains in the anode immediately after the discharge of the tenthcycle.

In some embodiments, the anisotropic force and the electrochemical cellmay be configured such that, when the electrochemical cell is fullycycled 10 times, the anode has a sheet resistance of less than 1000Ω/sq. immediately after the discharge of the tenth cycle, and 75 wt % orless of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the tenth cycle.

In some embodiments, the at least one non-lithium metal may be presentat a sufficient volume such that, when the electrochemical cell is fullycycled 10 times, the at least one non-lithium metal forms a regionhaving a sheet resistance of less than 1000 Ω/sq. immediately after thedischarge of the tenth cycle, and 75 wt % or less of the amount oflithium present in the anode in its initial fully-charged state remainsin the anode immediately after the discharge of the tenth cycle.

In one aspect, an electrochemical cell is described. The electrochemicalcell may comprise a cathode. The electrochemical cell may furthercomprise an anode comprising a solid solution of lithium and at leastone non-lithium metal, the anode having an active surface. Theelectrochemical cell may be configured such that it is in a chargedstate when it is first assembled. The electrochemical cell may be underan applied anisotropic force having a force component normal to theactive surface of the anode.

In some embodiments, the anisotropic force and the electrochemical cellmay be configured such that, when the electrochemical cell is fullycycled 50 times, the anode has a porosity of less than 20% immediatelyafter the discharge of the 50th cycle, and 75 wt % or less of the amountof lithium present in the anode in its initial fully-charged stateremains in the anode immediately after the discharge of the 50th cycle.

In some embodiments, the at least one non-lithium metal may be presentat a sufficient volume such that, when the electrochemical cell is fullycycled 50 times, the anode has a porosity of less than 20% immediatelyafter the discharge of the 50th cycle, and 75 wt % or less of the amountof lithium present in the anode in its initial fully-charged stateremains in the anode immediately after the discharge of the 50th cycle.

In some embodiments, the anisotropic force and the electrochemical cellmay be configured such that, when the electrochemical cell is fullycycled 50 times, the anode has a sheet resistance of less than 1000Ω/sq. immediately after the discharge of the 50th cycle, and 75 wt % orless of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the 50th cycle.

In some embodiments, the at least one non-lithium metal may be presentat a sufficient volume such that, when the electrochemical cell is fullycycled 50 times, the at least one non-lithium metal forms a regionhaving a sheet resistance of less than 1000 Ω/sq. immediately after thedischarge of the 50th cycle, and 75 wt % or less of the amount oflithium present in the anode in its initial fully-charged state remainsin the anode immediately after the discharge of the 50th cycle.

In one aspect, an electrochemical cell is described. The electrochemicalcell may comprise a cathode. The electrochemical cell may furthercomprise an anode comprising a solid solution of lithium and at leastone non-lithium metal, the anode having an active surface. Theelectrochemical cell may be configured such that it is in a chargedstate when it is first assembled. The electrochemical cell may be underan applied anisotropic force having a force component normal to theactive surface of the anode. In some embodiments, the anisotropic forceand the electrochemical cell may be configured such that, when theelectrochemical cell is fully cycled 10 times, immediately after thedischarge of the tenth cycle, the anode has a porosity that is less than50% of the porosity that would be present in an equivalent cell withoutthe applied anisotropic force, immediately after the discharge of itstenth cycle.

In some embodiments, the at least one non-lithium metal may be presentat a sufficient volume such that, when the electrochemical cell is fullycycled 10 times, immediately after the discharge of the tenth cycle, theanode has a porosity that is less than 50% of the porosity that would bepresent in an equivalent cell without the at least one non-lithiummetal, immediately after the discharge of its tenth cycle.

In some embodiments, the anisotropic force and the electrochemical cellmay be configured such that, when the electrochemical cell is fullycycled 10 times, immediately after the discharge of the tenth cycle, theanode has a sheet resistance that is less than 50% of the sheetresistance that would be present in an equivalent cell without theapplied anisotropic force, immediately after the discharge of its tenthcycle.

In some embodiments, the at least one non-lithium metal may be presentat a sufficient volume such that, when the electrochemical cell is fullycycled 10 times, immediately after the discharge of the tenth cycle, theanode has a sheet resistance that is less than 50% of the sheetresistance that would be present in an equivalent cell without the atleast one non-lithium metal, immediately after the discharge of itstenth cycle.

Other advantages and novel features of the present invention will becomeapparent from the following detailed description of various non-limitingembodiments of the invention when considered in conjunction with theaccompanying figures. In cases where the present specification and adocument incorporated by reference include conflicting and/orinconsistent disclosure, the present specification shall control.

BRIEF DESCRIPTION OF THE DRAWINGS

Non-limiting embodiments of the present invention will be described byway of example with reference to the accompanying figures, which areschematic and are not intended to be drawn to scale. In the figures,each identical or nearly identical component illustrated is typicallyrepresented by a single numeral. For purposes of clarity, not everycomponent is labeled in every figure, nor is every component of eachembodiment of the invention shown where illustration is not necessary toallow those of ordinary skill in the art to understand the invention. Inthe figures:

FIG. 1 shows a schematic diagram of a cross-section of anelectrochemical cell according to one set of embodiments of theinvention;

FIG. 2 shows a schematic diagram of an electrode of an electrochemicalcell according to one set of embodiments of the invention;

FIG. 3A shows an image of a comparative electrochemical cell at the endof a life cycle; and

FIG. 3B shows an image of an electrochemical cell, according to anembodiment of the invention, at the end of a life cycle.

DETAILED DESCRIPTION

Electrochemical cells (e.g., rechargeable lithium batteries) comprisingelectrodes comprising lithium (e.g., in the form of a solid solutionwith non-lithium metals), from which in situ current collectors may beformed, are generally described. Certain embodiments of the presentinvention are related to inventive arrangements of materials inlithium-containing electrodes and/or inventive uses of such electrodes.In some embodiments, one or more non-lithium components of thelithium-containing electrode can be used as a current collector. Thecurrent collector, when thus formed, can be positioned within theoriginal volume of the electrode, prior to the removal of lithium-basedelectrode active material during discharge. Use in this manner caneliminate the need for a separate, standalone current collector, whichcan, according to certain embodiments, lead to increases in energydensity and/or specific energy of the electrochemical cell in which suchelectrodes are employed.

Examples of electrochemical cells in which the present invention may bepracticed, include, without limitation, lithium-ion (Li-ion),lithium-sulfur (Li-S) and lithium-air (Li-air) batteries. In someembodiments, the electrochemical cells may be rechargeableelectrochemical cells (also referred to as secondary electrochemicalcells).

A lithium metal solid solution may be used, according to certainembodiments, as an anode or a partial anode. Use of such solid solutionsmay, according to certain embodiments, overcome certain disadvantagesresulting from localized lithium depletion in lithium-based batteries,without the need to employ an additional current collector. During cellcycling, lithium is stripped from the anode during a discharge stage andredeposited at the anode during a charge stage. According to one or moreembodiments of the present invention, however, the non-lithium metalcomponent is able to form a solid solution with residual lithium atambient temperature, and remains as an intact, electrically continuouscurrent collector regardless of state of charge or degree of lithiumdepletion.

According to one or more embodiments, the disclosed electrode (e.g.,anode) comprising a solid solution of lithium and at least onenon-lithium metal is incorporated into an electrochemical cell. The cellmay further comprise a cathode. The cathode and the anode may each havean active surface. The cell may comprise an electrolyte inelectrochemical communication with the cathode and the anode. Anelectrolyte is in electrochemical communication with an anode and acathode when it is capable of shuttling ions between the anode and thecathode during discharge of the electrochemical cell. The cell maycomprise a separator proximate to the electrolyte, as discussed furtherbelow. In the embodiments described herein, electrochemical cells (e.g.,rechargeable batteries) may undergo a charge/discharge cycle involvingdeposition of an electrode active material (e.g., lithium metal) on orin the anode during charging and removal of the electrode activematerial from the anode during discharging. During at least one periodof operation, the electrochemical cell may be under an appliedanisotropic force having a force component normal to the active surfaceof the anode.

In some embodiments, the electrochemical cell is configured such that itis in a charged state when it is first assembled. For example, in someembodiments, electrochemical cells in which the cathode is notlithium-based (such as a sulfur-based cathode) are in a charged statewhen first assembled. In some embodiments, the electrochemical cell isconfigured such that it is in a discharged state when it is firstassembled. For example, in some embodiments, electrochemical cells inwhich the cathode is lithium-based (such as a lithium intercalationcathode) are in a discharged state when first assembled.

As would be understood by a person of ordinary skill in the art, a cellis considered to be in a charged state when first assembled when it isfully or predominantly (i.e., greater than 50%) charged when it is firstassembled. In certain embodiments, it is advantageous to employ a cellthat is in a fully charged state when it is first assembled.

Likewise, a cell is considered to be in a discharged state when firstassembled when it is fully or predominantly (i.e., greater than 50%)discharged when first assembled. In certain embodiments, it isadvantageous to employ a cell that is in a fully discharged state whenit is first assembled.

During operation, the electrochemical cell may undergo a series ofcharge/discharge cycles. It should be understood that a full cycle ismade up of a complete charge followed by a complete discharge. Forexample, in embodiments in which the cell is assembled in a dischargedstate (e.g., cells having a lithium intercalation cathode), the firstfull cycle is complete after undergoing a first complete charge,followed by a first complete discharge. However, in embodiments, inwhich the cell is assembled in a charged state (e.g., cells having asulfur-based cathode), the first full cycle is completed after a firstcomplete discharge that follows either no charging step (if the cell wasfully charged at first assembly) or that follows a partial charging step(if the cell was partially discharged at first assembly).

As used herein, the term “initial fully-charged state” refers to thefirst fully charged state of an electrochemical cell. For example, inembodiments where the cell is assembled in a fully charged state, theinitial fully-charged state is the state at the completion of assembly.However, in embodiments where the cell is assembled in a dischargedstate (e.g., in a fully discharged state or in a predominantlydischarged state) or in a charged state that is not a fully chargedstate, the initial fully charged state is the state upon the first fullcharge following assembly.

In some embodiments, the anisotropic force and the electrochemical cellare configured to provide a beneficial reduction in porosity in theanode, as measured after undergoing a given number of charge/dischargecycles. The term “porosity” refers to a value of a material calculatedby dividing the pore volume of the material by the sum of the porevolume and the material volume, as would be understood by a person ofordinary skill in the art. The term “true density” refers to a densityvalue of a material calculated by dividing the mass of the material bythe volume of the material after subtracting out the pore volume, aswould be understood by a person of ordinary skill in the art. The term“bulk density” refers to a density value of a material calculated bydividing the mass of the material by the volume of the materialincluding the pore volume. These terms are further described, herein,with reference to the figures.

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a charged statewhen it is first assembled), the anisotropic force and theelectrochemical cell are configured such that, when the electrochemicalcell is fully cycled 10 times, the anode has a porosity of less than 20%immediately after the discharge of the tenth cycle, and, also, 75 wt %or less of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the tenth cycle. In other words, an anode having a porosity of lessthan 20% would have a pore volume that is less than 20% of the combinedpore volume and material volume of the anode.

By way of example, if an anode contains 10 microns of lithium in itsfirst fully charged state (e.g., as assembled, in some embodiments, orwhen first charged after assembly, in others), and contains 7.5 micronsof lithium immediately after the discharge of the tenth cycle, then 75wt % of the amount of lithium present in the anode in its initialfully-charged state has remained in the anode immediately after thedischarge of the tenth cycle. This percentage may be determined bymeasuring the amount of lithium in the anode when it is in its firstfully charged state (either at assembly, or after the first chargingsubsequent to assembly). The cell may then undergo a series ofcharge/discharge cycles, and after a set point (for example, immediatelyafter the discharge of the tenth cycle), the amount of lithium in theanode is again measured. The comparison of the second value with theinitial value may then be used to determine the wt % difference.

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a charged statewhen it is first assembled), the anisotropic force and theelectrochemical cell are configured such that, when the electrochemicalcell is fully cycled 10 times, the anode has a porosity of less than15%, 10%, 5%, or 1% immediately after the discharge of the tenth cycle.In some embodiments, the anisotropic force and the electrochemical cellare configured such that, when the electrochemical cell is fully cycled10 times, 60 wt % or less, 50 wt % or less, 40 wt % or less, 30 wt % orless, 20 wt % or less, or 10 wt % or less of the amount of lithiumpresent in the anode in its initial fully-charged state remains in theanode immediately after the discharge of the tenth cycle.

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a discharged statewhen it is first assembled), the anisotropic force and theelectrochemical cell are configured such that, when the electrochemicalcell is fully cycled 50 times, the anode has a porosity of less than 20%immediately after the discharge of the 50th cycle, and, also, 75 wt % orless of the amount of lithium present in the anode in its initialfully-charged state (e.g., upon its first full charge subsequent toassembly, if assembled not in a fully charged state) remains in theanode immediately after the discharge of the 50th cycle. In someembodiments, the anisotropic force and the electrochemical cell areconfigured such that, when the electrochemical cell is fully cycled 50times, the anode has a porosity of less than 15%, 10%, 5%, or 1%immediately after the discharge of the 50th cycle. In some embodiments,the anisotropic force and the electrochemical cell are configured suchthat, when the electrochemical cell is fully cycled 50 times, 60 wt % orless, 50 wt % or less, 40 wt % or less, 30 wt % or less, 20 wt % orless, or 10 wt % or less of the amount of lithium present in the anodein its initial fully-charged state remains in the anode immediatelyafter the discharge of the 50th cycle.

In some embodiments, the anisotropic force and the electrochemical cellare configured such that, when the electrochemical cell is fully cycled10 times, immediately after the discharge of the tenth cycle, the anodehas a porosity that is less than 50% of the porosity that would bepresent in an equivalent cell without the applied anisotropic force,immediately after the discharge of its tenth cycle. In some embodiments,the anisotropic force and the electrochemical cell are configured suchthat, when the electrochemical cell is fully cycled 10 times,immediately after the discharge of the tenth cycle, the anode has aporosity of less than 40%, 30%, 20%, or 10% of the porosity that wouldbe present in an equivalent cell without the applied anisotropic force,immediately after the discharge of its tenth cycle.

In some embodiments, the at least one non-lithium metal is present at asufficient volume to provide a beneficial reduction in porosity in theanode, as measured after undergoing a given number of charge/dischargecycles.

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a charged statewhen it is first assembled), the at least one non-lithium metal ispresent at a sufficient volume such that, when the electrochemical cellis fully cycled 10 times, the anode has a porosity of less than 20%immediately after the discharge of the tenth cycle, and, also, 75 wt %or less of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the tenth cycle. In some embodiments, the at least one non-lithiummetal is present at a sufficient volume such that, when theelectrochemical cell is fully cycled 10 times, the anode has a porosityof less than 15%, 10%, 5%, or 1% immediately after the discharge of thetenth cycle. In some embodiments, the at least one non-lithium metal ispresent at a sufficient volume such that, when the electrochemical cellis fully cycled 10 times 60 wt % or less, 50 wt % or less, 40 wt % orless, 30 wt % or less, 20 wt % or less, or 10 wt % or less of the amountof lithium present in the anode in its initial fully-charged stateremains in the anode immediately after the discharge of the tenth cycle.

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a discharged statewhen it is first assembled), the at least one non-lithium metal ispresent at a sufficient volume such that, when the electrochemical cellis fully cycled 50 times, the anode has a porosity of less than 20%immediately after the discharge of the 50^(th) cycle, and, also, 75 wt %or less of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the 50^(th) cycle. In some embodiments, the at least one non-lithiummetal is present at a sufficient volume such that, when theelectrochemical cell is fully cycled 50 times, the anode has a porosityof less than 15%, 10%, 5%, or 1% immediately after the discharge of the50^(th) cycle. In some embodiments, the at least one non-lithium metalis present at a sufficient volume such that, when the electrochemicalcell is fully cycled 50 times, 60 wt % or less, 50 wt % or less, 40 wt %or less, 30 wt % or less, 20 wt % or less, or 10 wt % or less of theamount of lithium present in the anode in its initial fully-chargedstate remains in the anode immediately after the discharge of the50^(th) cycle.

In some embodiments, the at least one non-lithium metal is present at asufficient volume such that, when the electrochemical cell is fullycycled 10 times, immediately after the discharge of the tenth cycle, theanode has a porosity that is less than 50% of the porosity that would bepresent in an equivalent cell without the at least one non-lithiummetal, immediately after the discharge of its tenth cycle. In someembodiments, the at least one non-lithium metal is present at asufficient volume such that, when the electrochemical cell is fullycycled 10 times, immediately after the discharge of the tenth cycle, theanode has a porosity of less than 40%, 30%, 20%, or 10% of the porositythat would be present in an equivalent cell without the at least onenon-lithium metal, immediately after the discharge of its tenth cycle.In some embodiments, the anisotropic force and the electrochemical cellare configured to provide a beneficial reduction in sheet resistance inthe anode, as measured after undergoing a given number ofcharge/discharge cycles. Sheet resistance is measured using a 4-pointprobe where a current is applied between 2 of the probes and the voltageis measured between the other 2 probes using a voltmeter (e.g., aLoresta-GP 4-point probe, commercially available from Mitsubishi).

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a charged statewhen it is first assembled), the anisotropic force and theelectrochemical cell are configured such that when the electrochemicalcell is fully cycled 10 times, the anode has a sheet resistance of lessthan 1000 Ω/sq. immediately after the discharge of the tenth cycle, and,also, 75 wt % or less of the amount of lithium present in the anode inits initial fully-charged state remains in the anode immediately afterthe discharge of the tenth cycle. In some embodiments, the anisotropicforce and the electrochemical cell are configured such that, when theelectrochemical cell is fully cycled 10 times, the anode has a sheetresistance of less than 900 Ω/sq., 800 Ω/sq., 700 Ω/sq., 600 Ω/sq., 500Ω/sq., 400 Ω/sq., 300 Ω/sq., 200 Ω/sq., or 100 Ω/sq. immediately afterthe discharge of the tenth cycle. In some embodiments, the anisotropicforce and the electrochemical cell are configured such that, when theelectrochemical cell is fully cycled 10 times, 60 wt % or less, 50 wt %or less, 40 wt % or less, 30 wt % or less, 20 wt % or less, or 10 wt %or less of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the tenth cycle.

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a discharged statewhen it is first assembled), the anisotropic force and theelectrochemical cell are configured such that, when the electrochemicalcell is fully cycled 50 times, the anode has a sheet resistance of lessthan 1000 Ω/sq. immediately after the discharge of the 50th cycle, and,also, 75 wt % or less of the amount of lithium present in the anode inits initial fully-charged state remains in the anode immediately afterthe discharge of the 50th cycle. In some embodiments, the anisotropicforce and the electrochemical cell are configured such that, when theelectrochemical cell is fully cycled 50 times, the anode has a sheetresistance of less than 900 Ω/sq., 800 Ω/sq., 700 Ω/sq., 600 Ω/sq., 500Ω/sq., 400 Ω/sq., 300 Ω/sq., 200 Ω/sq., or 100 Ω/sq. immediately afterthe discharge of the 50th cycle. In some embodiments, the anisotropicforce and the electrochemical cell are configured such that, when theelectrochemical cell is fully cycled 50 times, 60 wt % or less, 50 wt %or less, 40 wt % or less, 30 wt % or less, 20 wt % or less, or 10 wt %or less of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the 50th cycle.

In some embodiments, the anisotropic force and the electrochemical cellare configured such that, when the electrochemical cell is fully cycled10 times, immediately after the discharge of the tenth cycle, the anodehas a sheet resistance that is less than 50% of the sheet resistance ofan equivalent cell without the applied anisotropic force immediatelyafter the discharge of its tenth cycle. In some embodiments, theanisotropic force and the electrochemical cell are configured such that,when the electrochemical cell is fully cycled 10 times, immediatelyafter the discharge of the tenth cycle, the anode has a sheet resistanceof less than 40%, 30%, 20%, or 10% of the sheet resistance that would bepresent in an equivalent cell without the applied anisotropic forceimmediately after the discharge of its tenth cycle.

In some embodiments, the at least one non-lithium metal is present at asufficient volume to provide a beneficial reduction in sheet resistancein the anode, as measured after undergoing a given number ofcharge/discharge cycles.

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a charged statewhen it is first assembled), the at least one non-lithium metal ispresent at a sufficient volume such that, when the electrochemical cellis fully cycled 10 times, the anode has a sheet resistance of less than1000 Ω/sq. immediately after the discharge of the tenth cycle, and,also, 75 wt % or less of the amount of lithium present in the anode inits initial fully-charged state remains in the anode immediately afterthe discharge of the tenth cycle. In some embodiments, the at least onenon-lithium metal is present at a sufficient volume such that, when theelectrochemical cell is fully cycled 10 times, the anode has a sheetresistance of less than 900 Ω/sq., 800 Ω/sq., 700 Ω/sq., 600 Ω/sq., 500Ω/sq., 400 Ω/sq., 300 Ω/sq., 200 Ω/sq., or 100 Ω/sq. immediately afterthe discharge of the tenth cycle. In some embodiments, the at least onenon-lithium metal is present at a sufficient volume such that, when theelectrochemical cell is fully cycled 10 times, 60 wt % or less, 50 wt %or less, 40 wt % or less, 30 wt % or less, 20 wt % or less, or 10 wt %or less of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the tenth cycle.

In some embodiments (for example, in some embodiments in which theelectrochemical cell is configured such that it is in a discharged statewhen it is first assembled), the at least one non-lithium metal ispresent at a sufficient volume such that, when the electrochemical cellis fully cycled 50 times, the anode has a sheet resistance of less than1000 Ω/sq. immediately after the discharge of the 50th cycle, and, also,75 wt % or less of the amount of lithium present in the anode in itsinitial fully-charged state remains in the anode immediately after thedischarge of the 50th cycle. In some embodiments, the at least onenon-lithium metal is present at a sufficient volume such that, when theelectrochemical cell is fully cycled 50 times, the anode has a sheetresistance of less than 900 Ω/sq., 800 Ω/sq., 700 Ω/sq., 600 Ω/sq., 500Ω/sq., 400 Ω/sq., 300 Ω/sq., 200 Ω/sq., or 100 Ω/sq. immediately afterthe discharge of the 50th cycle. In some embodiments, the at least onenon-lithium metal is present at a sufficient volume such that, when theelectrochemical cell is fully cycled 50 times, 60 wt % or less, 50 wt %or less, 40 wt % or less, 30 wt % or less, 20 wt % or less, or 10 wt %or less of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the 50th cycle.

In some embodiments, the at least one non-lithium metal is present at asufficient volume such that, when the electrochemical cell is fullycycled 10 times, immediately after the discharge of the tenth cycle, theanode has a sheet resistance that is less than 50% of the sheetresistance that would be present in an equivalent cell without the atleast one non-lithium metal, immediately after the discharge of itstenth cycle. In some embodiments, the at least one non-lithium metal ispresent at a sufficient volume such that, when the electrochemical cellis fully cycled 10 times, immediately after the discharge of the tenthcycle, the anode has a sheet resistance of less than 40%, 30%, 20%, or10% of the sheet resistance that would be present in an equivalent cellwithout the at least one non-lithium metal, immediately after thedischarge of its tenth cycle.

In some embodiments, each of the electrodes comprise electrode activematerial. Electrode active materials are those materials associated withan electrode and which participate in the electrochemical reaction(s) ofthe electrochemical cell that generate electrical current. Cathodeactive materials are electrode active materials associated with thecathode of the electrochemical cell, and anode active materials areelectrode active materials associated with the anode of theelectrochemical cell.

FIG. 1 shows an example of an electrochemical cell 100, in which anelectrode (e.g., anode) 120, as described herein, may be incorporated.The electrochemical cell 100 includes a cathode 110, an electrolytelayer 130, and an anode 120. The anode 120 comprises a solid solution oflithium and at least one non-lithium metal. An active surface 185 of thecathode 110 is positioned at the interface of the cathode 110 and theelectrolyte 130. An active surface 186 of the anode 120 is positioned atthe interface of the anode 120 and electrolyte layer 130. In someembodiments, a current collector 180 is associated with the cathode 110.However, the incorporation of a solid solution in the anode 120 allowsfor the elimination of a separate current collector associated with theanode 120. Instead, a current collector is formed in situ from materialin the anode 120. The electrochemical cell 100 may be situated in anoptional enclosed containment structure 170.

In some embodiments described herein, a force, or forces, is (are)applied to portions of an electrochemical cell. Such application offorce may reduce irregularity or roughening of an electrode surface ofthe cell, thereby improving performance. Electrochemical cells in whichanisotropic forces are applied and methods for applying such forces aredescribed, for example, in U.S. Pat. No. 9,105,938, issued Aug. 11,2015, published as U.S. Patent Publication No. 2010/0035128 on Feb. 11,2010, and entitled “Application of Force in Electrochemical Cells,”which is incorporated herein by reference in its entirety for allpurposes.

The force may comprise, in some instances, an anisotropic force with acomponent normal to an active surface of the anode of theelectrochemical cell. In the embodiments described herein,electrochemical cells (e.g., rechargeable batteries) may undergo acharge/discharge cycle involving deposition of an electrode activematerial (e.g., lithium metal) on or in the anode during charging andremoval of the electrode active material from the anode duringdischarging. The uniformity with which the metal is deposited on theanode may affect cell performance. For example, when lithium metal isremoved from and/or redeposited on an anode, it may, in some cases,result in an uneven surface. For example, upon redeposition it maydeposit unevenly forming a rough surface. The roughened surface mayincrease the amount of lithium metal available for undesired chemicalreactions which may result in decreased cycling lifetime and/or poorcell performance. The application of force to the electrochemical cellhas been found, in accordance with certain embodiments described herein,to reduce such behavior and to improve the cycling lifetime and/orperformance of the cell. In some embodiments, the electrochemical cellis capable of being cycled at least 70 times before its capacity in acharged state is reduced to less than 80% of an original chargecapacity.

Referring to FIG. 1, a force may be applied in the direction of arrow181. Arrow 182 illustrates the component of force 181 that is normal toactive surface 185 of cathode 110 and active surface 186 of anode 120.In the case of a curved surface, for example, a concave surface or aconvex surface, the force may comprise an anisotropic force with acomponent normal to a plane that is tangent to the curved surface at thepoint at which the force is applied.

In some embodiments, an anisotropic force with a component normal to anactive surface of the anode is applied during at least one period oftime during charge and/or discharge of the electrochemical cell. In someembodiments, the force may be applied continuously, over one period oftime, or over multiple periods of time that may vary in duration and/orfrequency. The anisotropic force may be applied, in some cases, at oneor more pre-determined locations, optionally distributed over an activesurface of the anode. In some embodiments, the anisotropic force isapplied uniformly over one or more active surfaces of the anode.

An “anisotropic force” is given its ordinary meaning in the art andmeans a force that is not equal in all directions. A force equal in alldirections is, for example, internal pressure of a fluid or materialwithin the fluid or material, such as internal gas pressure of anobject. Examples of forces not equal in all directions include forcesdirected in a particular direction, such as the force on a table appliedby an object on the table via gravity. Another example of an anisotropicforce includes certain forces applied by a band arranged around aperimeter of an object. For example, a rubber band or turnbuckle canapply forces around a perimeter of an object around which it is wrapped.However, the band may not apply any direct force on any part of theexterior surface of the object not in contact with the band. Inaddition, when the band is expanded along a first axis to a greaterextent than a second axis, the band can apply a larger force in thedirection parallel to the first axis than the force applied parallel tothe second axis.

A force with a “component normal” to a surface, for example an activesurface of an anode, is given its ordinary meaning as would beunderstood by those of ordinary skill in the art and includes, forexample, a force which at least in part exerts itself in a directionsubstantially perpendicular to the surface. Those of ordinary skill canunderstand other examples of these terms, especially as applied withinthe description of this document.

FIG. 2 shows a view of the surface of the anode 120 of theelectrochemical cell 100 of FIG. 1, after the electrochemical cell 100has been fully cycled for a number of cycles, for example, ten times,and immediately after a full discharge. In such a state, most of thelithium portion (e.g., at least 60%, 70%, 80%, 90%, or greater) of thesolid solution 124 is removed from the anode 120, with the remainingsolid solution functioning as an in situ current collector, formedprimarily by the remaining non-lithium metal component of the anode 120.In some embodiments, 75 wt % or less, 60 wt % or less, 50 wt % or less,40 wt % or less, 30 wt % or less, 20 wt % or less, or 10 wt % or less ofthe amount of lithium present in the anode 120 in its initialfully-charged state remains in the anode 120 immediately after thedischarge of the tenth cycle. In some embodiments, 75 wt % or less, 60wt % or less, 50 wt % or less, 40 wt % or less, 30 wt % or less, 20 wt %or less, or 10 wt % or less of the amount of lithium present in theanode 120 in its initial fully-charged state remains in the anode 120immediately after the discharge of the 50th cycle. In this state, anumber of pores 126 are also present in the anode 120. The pores 126form a pore volume. The anode 120 has a porosity calculated by dividingthe volume of the pores 126 by the sum of the pore volume 126 and thevolume of the solid solution 124 forming anode 120. The solid solution124 forms a material volume. The solid solution 124 has a bulk densitycalculated by dividing the mass of the material 124 by the volume of thematerial 124 including the volume of the pores 126. The solid solution124 has a true density calculated by dividing the mass of material 124by the volume of material 124 after subtracting out the volume of pores126.

In the discharged state shown in FIG. 2, an anisotropic force 181 (shownin FIG. 1) is applied having a force component 182 normal to the activesurface of the anode 120, as described above with regard to FIG. 1. Inthis discharged state, the cell 100 and the anisotropic force 181 areconfigured such that the anode 120 has a pore volume of less than 20%.In this discharged state, the anisotropic force 181 is configured suchthat the anode 120 has a bulk density that is at least 80% of its bulkdensity. Other values for pore volume or bulk density are also possible,as described above. In this discharged state, the non-lithium metal ispresent in the solid solution 124 at a sufficient volume to provide ananode 120 having a pore volume of less than 20%.

In the fully discharged state shown in FIG. 2, the cell 100 and theanisotropic force 181 are configured such that the anode 120 (e.g., thein situ current collector) formed by the solid solution 124 has a sheetresistance of less than 1000 Ω/sq. The non-lithium metal is present inthe solid solution 124 at a sufficient volume to provide an anode 120having a sheet resistance of less than 1000 Ω/sq. Other values for thesheet resistance are also possible, as described above. In thedischarged state shown in FIG. 2, 75 wt % or less of the amount oflithium present in the anode 120 in its initial fully-charged stateremains in the anode 120.

Those of ordinary skill in the art are familiar with solid solutions inthe context of metal materials, which generally refer to arrangements inwhich two or more metals are mixed within a solid state material. Asused herein, the term “solid solution” refers to a homogeneous mixtureof two or more kinds of metals occurring in the solid state, and isdistinguished from an intermetallic compound, whose crystal structurediffers from that of the individual constituents, or other types ofalloys. In some embodiments, a solid solution comprises a compound inwhich a first component is present within the interstices of the crystalstructure of a second component. The solid solution may be a singlephase solid solution.

According to one or more embodiments, the one or more non-lithium metalschosen to form the solid solution with lithium may be selected accordingto certain criteria, as follows.

In some embodiments, the non-lithium metal is not electrochemicallyactive in the cell operating voltage window (e.g., from about 0 V toabout 5 V). In some embodiments, less than about 25 wt %, less thanabout 10 wt %, less than about 5 wt %, or less than about 1 wt % of theat least one non-lithium metal participates in an electrochemicalreaction during a first charge and discharge cycle of the cell operatingwithin the above listed voltage window, as determined throughenergy-dispersive x-ray spectroscopy (EDS) analysis.

In some embodiments, the non-lithium metal is not reactive with theelectrolyte. In some embodiments, non-reactivity with the electrolyteallows the non-lithium metal to remain as an intact current collector.In some embodiments, less than about 25 wt %, less than about 10 wt %,less than about 5 wt %, or less than about 1 wt % of the at least onenon-lithium metal participates in a chemical reaction with theelectrolyte, as determined through EDS analysis.

In some embodiments, the solid solution may have a relatively low yieldstrength. For example, the solid solution may have a yield strength offrom 0.1 to 100 MPa, or of from 0.4 to 40 MPa. In some embodiments, theincorporation of a solid solution having such a yield strength aids inthe formation of a substantially continuous sheet of non-lithiummaterial within the cell to serve as an in situ current collector. Insome embodiments, the solid solution has a yield strength between thatof the lithium and the non-lithium component. Yield strength may bemeasured by a mechanical tester (such as one commercially available fromINSTRON) or by a hardness tester following the testing protocoldescribed in ASTM E2546.

In some embodiments, the amount of non-lithium metal may be present inthe anode in an amount sufficient to form a substantially continuoussheet. In some embodiments, the amount of non-lithium metal may bepresent in the anode in an amount sufficient to form a currentcollector. In some embodiments, the amount of non-lithium metal presentin the anode is otherwise minimized so to increase the energy densityand/or specific energy of the electrochemical cell. Such an arrangementallows for the formation of an in situ current collector whileoptimizing the energy density of the electrode. In some embodiments, thenon-lithium metal in the anode is equal to or less than 25 wt %, 10 wt%, 5 wt % or 1 wt % of the combined weight of lithium and non-lithiummetal in the anode during a fully charged state. In some embodiments,the non-lithium metal in the anode is at least 0.1 wt %, 1 wt %, 5 wt %or 10 wt % of the combined weight of lithium and non-lithium metal inthe anode during a fully charged state. In some embodiments, thenon-lithium metal in the anode is equal to or less than 25 wt %, 10 wt%, 5 wt % or 1 wt % of the combined weight of lithium and non-lithiummetal in the anode during a fully charged state, as assembled. In someembodiments, the non-lithium metal in the anode is at least 0.1 wt %, 1wt %, 5 wt % or 10 wt % of the combined weight of lithium andnon-lithium metal in the anode during a fully charged state, asassembled. In some embodiments, the non-lithium metal in the anode isequal to or less than 25 wt %, 10 wt %, 5 wt % or 1 wt % of the combinedweight of lithium and non-lithium metal in the anode during its firstfully charged state after assembly. In some embodiments, the non-lithiummetal in the anode is at least 0.1 wt %, 1 wt %, 5 wt % or 10 wt % ofthe combined weight of lithium and non-lithium metal in the anode duringits first fully charged state after assembly. Combinations of theseranges are also possible.

In some embodiments, the non-lithium metal forms a solid solution withlithium at ambient temperature. In some embodiments, the non-lithiummetal forms a solid solution with lithium at a temperature of between−40° C. and 80° C. In some embodiments, the non-lithium metal forms asolid solution with lithium in the cell during cycling and remains as anintact current collector.

In some embodiments, the at least one non-lithium metal is selected fromthe group consisting of magnesium, zinc, lead, tin, platinum, gold,aluminum, cadmium, silver, mercury, palladium, gallium, sodium,potassium, rubidium, cesium, francium, and combinations thereof. In someembodiments, the at least one non-lithium metal is selected from thegroup consisting of magnesium, zinc, lead, tin, platinum, gold,aluminum, cadmium, silver, mercury, and combinations thereof. In someembodiments, the at least one non-lithium metal is selected from thegroup consisting of magnesium, zinc, lead, platinum, gold, cadmium,silver, mercury, and combinations thereof.

In some embodiments, the at least one non-lithium metal comprises orconsists essentially of magnesium. In some embodiments, the at least onenon-lithium metal comprises or consists essentially of zinc. In someembodiments, the at least one non-lithium metal comprises or consistsessentially of lead. In some embodiments, the at least one non-lithiummetal comprises or consists essentially of tin. In some embodiments, theat least one non-lithium metal comprises or consists essentially ofplatinum. In some embodiments, the at least one non-lithium metalcomprises or consists essentially of gold. In some embodiments, the atleast one non-lithium metal comprises or consists essentially ofaluminum. In some embodiments, the at least one non-lithium metalcomprises or consists essentially of cadmium. In some embodiments, theat least one non-lithium metal comprises or consists essentially ofsilver. In some embodiments, the at least one non-lithium metalcomprises or consists essentially of mercury. In some embodiments, theat least one non-lithium metal comprises or consists essentially ofpalladium. In some embodiments, the at least one non-lithium metalcomprises or consists essentially of gallium. In some embodiments, theat least one non-lithium metal comprises or consists essentially ofsodium. In some embodiments, the at least one non-lithium metalcomprises or consists essentially of potassium. In some embodiments, theat least one non-lithium metal comprises or consists essentially ofrubidium. In some embodiments, the at least one non-lithium metalcomprises or consists essentially of cesium. In some embodiments, the atleast one non-lithium metal comprises or consists essentially offrancium.

In some embodiments the at least one non-lithium metal excludes thegroup consisting of silicon, germanium, tin, antimony, bismuth, andaluminum. In some embodiments, the at least one non-lithium metalexcludes silicon. In some embodiments, the at least one non-lithiummetal excludes germanium. In some embodiments, the at least onenon-lithium metal excludes tin. In some embodiments, the at least onenon-lithium metal excludes antimony. In some embodiments, the at leastone non-lithium metal excludes bismuth. In some embodiments, the atleast one non-lithium metal excludes aluminum.

It is to be understood that one or more non-lithium metals can be used.That is, the non-lithium component of the solid solution can be a singlemetal or a combination of two or more metals.

Anodes described herein, such as lithium and non-lithium metal solidsolutions, may be formed by any suitable method. Such methods mayinclude, for example, physical deposition methods, chemical vapordeposition methods, plasma enhanced chemical vapor depositiontechniques, thermal evaporation (e.g., resistive, inductive, radiation,and electron beam heating), sputtering (e.g., diode, DC magnetron, RF,RF magnetron, pulsed, dual magnetron, AC, FM, and reactive sputtering),jet vapor deposition, laser ablation, extrusion, electroplating, ionplating, and cathodic arc. In some instances, Li vapor and a vapor ofthe non-lithium metal are co-deposited (simultaneously) onto asubstrate, e.g., using methods such as those mentioned above, to formthe solid solution anode. Deposition can be carried out in a vacuum orinert atmosphere.

As used herein, “cathode” refers to the electrode in which an electrodeactive material is oxidized during charging and reduced duringdischarging, and “anode” refers to the electrode in which an electrodeactive material is reduced during charging and oxidized duringdischarging.

As noted above, the anode can comprise an anode active material. Forexample, referring to FIG. 1, anode 120 of electrochemical cell 100comprises an anode active material. In some embodiments, the anodeactive material comprises lithium (e.g., lithium metal) in solidsolution with at least one non-lithium metal. Potential candidates forthe at least one non-lithium metal are discussed above.

In some embodiments, the anode active material contains at least 50 wt %lithium. In some cases, the anode active material contains at least 75wt %, at least 90 wt %, at least 95 wt %, or at least 99 wt % lithium.

In some embodiments, the anode comprises lithium ions which areliberated during discharge and which are integrated (e.g., intercalated)into the anode during charge. In some embodiments, the anode activematerial is a lithium intercalation compound (e.g., a compound that iscapable of reversibly inserting lithium ions at lattice sites and/orinterstitial sites). In certain embodiments, the anode active materialcomprises lithium titanate (Li₄Ti₅O₁₂, also referred to as “LTO”),tin-cobalt oxide, or any combinations thereof.

As noted above, the cathode can comprise a cathode active material. Forexample, referring to FIG. 1, cathode 110 of electrochemical cell 100comprises a cathode active material. A variety of cathode activematerials are suitable for use with cathodes of the electrochemicalcells described herein, according to certain embodiments. In someembodiments, the cathode active material comprises a lithiumintercalation compound (e.g., a compound that is capable of reversiblyinserting lithium ions at lattice sites and/or interstitial sites). Incertain cases, the cathode active material comprises a layered oxide. Alayered oxide generally refers to an oxide having a lamellar structure(e.g., a plurality of sheets, or layers, stacked upon each other).Non-limiting examples of suitable layered oxides include lithium cobaltoxide (LiCoO₂), lithium nickel oxide (LiNiO₂), and lithium manganeseoxide (LiMnO₂). In some embodiments, the layered oxide is lithium nickelmanganese cobalt oxide (LiNi_(x)Mn_(y)Co_(z)O₂, also referred to as“NMC” or “NCM”). In some such embodiments, the sum of x, y, and z is 1.For example, a non-limiting example of a suitable NMC compound isLiNi_(1/3)Mn_(1/3)Co_(1/3)O₂. In some embodiments, a layered oxide mayhave the formula (Li₂MnO₃)_(x)(LiMO₂)_((1−x)) where M is one or more ofNi, Mn, and Co. For example, the layered oxide may be(Li₂MnO₃)_(0.25)(LiNi_(0.3)Co_(0.15)Mn_(0.55)O₂)_(0.75). In someembodiments, the layered oxide is lithium nickel cobalt aluminum oxide(LiNi_(x)Co_(y)Al_(z)O₂, also referred to as “NCA”). In some suchembodiments, the sum of x, y, and z is 1. For example, a non-limitingexample of a suitable NCA compound is LiNi_(0.8)Co_(0.15)Al_(0.05)O₂. Incertain embodiments, the cathode active material is a transition metalpolyanion oxide (e.g., a compound comprising a transition metal, anoxygen, and/or an anion having a charge with an absolute value greaterthan 1). A non-limiting example of a suitable transition metal polyanionoxide is lithium iron phosphate (LiFePO₄, also referred to as “LFP”).Another non-limiting example of a suitable transition metal polyanionoxide is lithium manganese iron phosphate (LiMn_(x)Fe_(1−x)PO₄, alsoreferred to as “LMFP”). A non-limiting example of a suitable LMFPcompound is LiMn_(0.8)Fe_(0.2)PO₄. In some embodiments, the cathodeactive material is a spinel (e.g., a compound having the structureAB₂O₄, where A can be Li, Mg, Fe, Mn, Zn, Cu, Ni, Ti, or Si, and B canbe Al, Fe, Cr, Mn, or V). A non-limiting example of a suitable spinel isa lithium manganese oxide with the chemical formula LiM_(x)Mn_(2−x)O₄where M is one or more of Co, Mg, Cr, Ni, Fe, Ti, and Zn. In someembodiments, x may equal 0 and the spinel may be lithium manganese oxide(LiMn₂O₄, also referred to as “LMO”). Another non-limiting example islithium manganese nickel oxide (LiNi_(x)M_(2−x)O₄, also referred to as“LMNO”). A non-limiting example of a suitable LMNO compound isLiNi_(0.5)Mn_(1.5)O₄. In certain cases, the electroactive material ofthe second electrode comprises Li_(1.14)Mn_(0.42)Ni_(0.25)Co_(0.29)O₂(“HC-MNC”), lithium carbonate (Li₂CO₃), lithium carbides (e.g., Li₂C₂,Li₄C, Li₆C₂, Li₈C₃, Li₆C₃, Li₄C₃, Li₄C₅), vanadium oxides (e.g., V₂O₅,V₂O₃, V₆O₁₃), and/or vanadium phosphates (e.g., lithium vanadiumphosphates, such as Li₃V₂(PO₄)₃), or any combination thereof. In someembodiments, the cathode active material comprises a conversioncompound. For instance, the cathode may be a lithium conversion cathode.It has been recognized that a cathode comprising a conversion compoundmay have a relatively large specific capacity. Without wishing to bebound by a particular theory, a relatively large specific capacity maybe achieved by utilizing all possible oxidation states of a compoundthrough a conversion reaction in which more than one electron transfertakes place per transition metal (e.g., compared to 0.1-1 electrontransfer in intercalation compounds). Suitable conversion compoundsinclude, but are not limited to, transition metal oxides (e.g., Co₃O₄),transition metal hydrides, transition metal sulfides, transition metalnitrides, and transition metal fluorides (e.g., CuF₂, FeF₂, FeF₃). Atransition metal generally refers to an element whose atom has apartially filled d sub-shell (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu,Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt,Au, Hg, Rf, Db, Sg, Bh, Hs).

In some cases, the cathode active material may be doped with one or moredopants to alter the electrical properties (e.g., electricalconductivity) of the cathode active material. Non-limiting examples ofsuitable dopants include aluminum, niobium, silver, and zirconium.

In certain embodiments, the cathode active material comprises sulfur. Insome embodiments, the cathode active material comprises electroactivesulfur-containing materials. “Electroactive sulfur-containingmaterials,” as used herein, refers to electrode active materials whichcomprise the element sulfur in any form, wherein the electrochemicalactivity involves the oxidation or reduction of sulfur atoms ormoieties. As an example, the electroactive sulfur-containing materialmay comprise elemental sulfur (e.g., S₈). In some embodiments, theelectroactive sulfur-containing material comprises a mixture ofelemental sulfur and a sulfur-containing polymer. Thus, suitableelectroactive sulfur-containing materials may include, but are notlimited to, elemental sulfur, sulfides or polysulfides (e.g., of alkalimetals) which may be organic or inorganic, and organic materialscomprising sulfur atoms and carbon atoms, which may or may not bepolymeric. Suitable organic materials include, but are not limited to,those further comprising heteroatoms, conductive polymer segments,composites, and conductive polymers. In some embodiments, anelectroactive sulfur-containing material within an electrode (e.g., acathode) comprises at least about 40 wt % sulfur. In some cases, theelectroactive sulfur-containing material comprises at least about 50 wt%, at least about 75 wt %, or at least about 90 wt % sulfur.

Examples of sulfur-containing polymers include those described in: U.S.Pat. Nos. 5,601,947 and 5,690,702 to Skotheim et al.; U.S. Pat. Nos.5,529,860 and 6,117,590 to Skotheim et al.; U.S. Pat. No. 6,201,100issued Mar. 13, 2001, to Gorkovenko et al., and PCT Publication No. WO99/33130. Other suitable electroactive sulfur-containing materialscomprising polysulfide linkages are described in U.S. Pat. No. 5,441,831to Skotheim et al.; U.S. Pat. No. 4,664,991 to Perichaud et al., and inU.S. Pat. Nos. 5,723,230, 5,783,330, 5,792,575 and 5,882,819 to Naoi etal. Still further examples of electroactive sulfur-containing materialsinclude those comprising disulfide groups as described, for example in,U.S. Pat. No. 4,739,018 to Armand et al.; U.S. Pat. Nos. 4,833,048 and4,917,974, both to De Jonghe et al.; U.S. Pat. Nos. 5,162,175 and5,516,598, both to Visco et al.; and U.S. Pat. No. 5,324,599 to Oyama etal.

The cathode and/or anode may comprise, as noted above, pores, accordingto certain embodiments. As used herein, a “pore” refers to a pore asmeasured using ASTM D6583-00, which measures porosity by oil absorption,and generally refers to a conduit, void, or passageway, at least aportion of which is surrounded by the medium in which the pore is formedsuch that a continuous loop may be drawn around the pore while remainingwithin the medium. Generally, voids within a material that arecompletely surrounded by the material (and thus, not accessible fromoutside the material, e.g., closed cells) are not considered poreswithin the context of the invention. It should be understood that, incases where the article comprises an agglomeration of particles, poresinclude both the interparticle pores (i.e., those pores defined betweenparticles when they are packed together, e.g., interstices) andintraparticle pores (i.e., those pores lying within the envelopes of theindividual particles). Pores may comprise any suitable cross-sectionalshape such as, for example, circular, elliptical, polygonal (e.g.,rectangular, triangular, etc.), irregular, and the like.

As would be understood by a person of ordinary skill in the art, theporosity of an anode subjected to an anisotropic force, at the time ofimmediately after the discharge of the tenth cycle and after theelectrochemical cell is fully cycled 10 times, may be measured byapplying the above-described porosity test after removing the anode fromthe cell after which it is no longer subjected to the anisotropic force.Because removal of the anode causes no substantial change in the valueof the porosity of the anode as compared to when it was subjected to theanisotropic force within the cell, testing the anode by this procedureis indicative of the value of the porosity of the anode while it isincorporated in the cell under an applied anisotropic force.

As noted above, inventive electrochemical cells comprise an electrolyteand/or separator. For example, referring to FIG. 1, electrochemical cell100 comprises electrolyte 130. The electrolyte may comprise a separator.The electrolytes used in electrochemical or battery cells can functionas a medium for the storage and transport of ions, and in the specialcase of solid electrolytes and gel electrolytes, these materials mayadditionally function as a separator between the anode and the cathode.Any liquid, solid, or gel material capable of storing and transportingions may be used, so long as the material facilitates the transport ofions (e.g., lithium ions) between the anode and the cathode. Theelectrolyte is electronically non-conductive to prevent short circuitingbetween the anode and the cathode. In some embodiments, the electrolytemay comprise a non-solid electrolyte.

In some embodiments, the electrolyte comprises a fluid that can be addedat any point in the fabrication process. In some cases, theelectrochemical cell may be fabricated by providing a cathode and ananode, applying an anisotropic force component normal to the activesurface of the anode, and subsequently adding the fluid electrolyte suchthat the electrolyte is in electrochemical communication with thecathode and the anode. In other cases, the fluid electrolyte may beadded to the electrochemical cell prior to or simultaneously with theapplication of the anisotropic force component, after which theelectrolyte is in electrochemical communication with the cathode and theanode.

The electrolyte can comprise one or more ionic electrolyte salts toprovide ionic conductivity and one or more liquid electrolyte solvents,gel polymer materials, or polymer materials. Suitable non-aqueouselectrolytes may include organic electrolytes comprising one or morematerials selected from the group consisting of liquid electrolytes, gelpolymer electrolytes, and solid polymer electrolytes. Examples ofnon-aqueous electrolytes for lithium batteries are described by Dornineyin Lithium Batteries, New Materials, Developments and Perspectives,Chapter 4, pp. 137-165, Elsevier, Amsterdam (1994). Examples of gelpolymer electrolytes and solid polymer electrolytes are described byAlamgir et al. in Lithium Batteries, New Materials, Developments andPerspectives, Chapter 3, pp. 93-136, Elsevier, Amsterdam (1994).Heterogeneous electrolyte compositions that can be used in batteriesdescribed herein are described in U.S. patent application Ser. No.12/312,764, filed May 26, 2009 and entitled “Separation ofElectrolytes,” by Mikhaylik et al., which is incorporated herein byreference in its entirety.

Examples of useful non-aqueous liquid electrolyte solvents include, butare not limited to, non-aqueous organic solvents, such as, for example,N-methyl acetamide, acetonitrile, acetals, ketals, esters, carbonates,sulfones, sulfites, sulfolanes, aliphatic ethers, cyclic ethers, glymes,polyethers, phosphate esters, siloxanes, dioxolanes,N-alkylpyrrolidones, substituted forms of the foregoing, and blendsthereof. Fluorinated derivatives of the foregoing are also useful asliquid electrolyte solvents.

In some cases, aqueous solvents can be used as electrolytes, forexample, in lithium cells. Aqueous solvents can include water, which cancontain other components such as ionic salts. As noted above, in someembodiments, the electrolyte can include species such as lithiumhydroxide, or other species rendering the electrolyte basic, so as toreduce the concentration of hydrogen ions in the electrolyte.

Liquid electrolyte solvents can also be useful as plasticizers for gelpolymer electrolytes, i.e., electrolytes comprising one or more polymersforming a semi-solid network. Examples of useful gel polymerelectrolytes include, but are not limited to, those comprising one ormore polymers selected from the group consisting of polyethylene oxides,polypropylene oxides, polyacrylonitriles, polysiloxanes, polyimides,polyphosphazenes, polyethers, sulfonated polyimides, perfluorinatedmembranes (NAFION resins), polydivinyl polyethylene glycols,polyethylene glycol diacrylates, polyethylene glycol dimethacrylates,polysulfones, polyethersulfones, derivatives of the foregoing,copolymers of the foregoing, crosslinked and network structures of theforegoing, and blends of the foregoing, and optionally, one or moreplasticizers. In some embodiments, a gel polymer electrolyte comprisesbetween 10-20%, 20-40%, between 60-70%, between 70-80%, between 80-90%,or between 90-95% of a heterogeneous electrolyte by volume.

In some embodiments, one or more solid polymers can be used to form anelectrolyte. Examples of useful solid polymer electrolytes include, butare not limited to, those comprising one or more polymers selected fromthe group consisting of polyethers, polyethylene oxides, polypropyleneoxides, polyimides, polyphosphazenes, polyacrylonitriles, polysiloxanes,derivatives of the foregoing, copolymers of the foregoing, crosslinkedand network structures of the foregoing, and blends of the foregoing.

In addition to electrolyte solvents, gelling agents, and polymers asknown in the art for forming electrolytes, the electrolyte may furthercomprise one or more ionic electrolyte salts, also as known in the art,to increase the ionic conductivity.

Examples of ionic electrolyte salts for use in the electrolytes of thepresent invention include, but are not limited to, LiSCN, LiBr, LiI,LiClO₄, LiAsF₆, LiSO₃CF₃, LiSO₃CH₃, LiBF₄, LiB(Ph)₄, LiPF₆,LiC(SO₂CF₃)₃, LiN(SO₂CF₃)₂, and lithium bis(fluorosulfonyl)imide(LiFSI). Other electrolyte salts that may be useful include lithiumpolysulfides (Li₂S_(x)), and lithium salts of organic polysulfides(LiS_(x)R)_(a), where x is an integer from 1 to 20, n is an integer from1 to 3, and R is an organic group, and those disclosed in U.S. Pat. No.5,538,812 to Lee et al.

In some embodiments, the electrolyte comprises one or more roomtemperature ionic liquids. The room temperature ionic liquid, ifpresent, typically comprises one or more cations and one or more anions.Non-limiting examples of suitable cations include lithium cations and/orone or more quaternary ammonium cations such as imidazolium,pyrrolidinium, pyridinium, tetraalkylammonium, pyrazolium, piperidinium,pyridazinium, pyrimidinium, pyrazinium, oxazolium, and trizoliumcations. Non-limiting examples of suitable anions includetrifluromethylsulfonate (CF₃SO₃ ⁻), bis (fluorosulfonyl)imide (N(FSO₂)₂⁻, bis (trifluoromethyl sulfonyl)imide ((CF₃SO₂)₂N⁻, bis(perfluoroethylsulfonyl)imide((CF₃CF₂SO₂)₂N⁻ andtris(trifluoromethylsulfonyl)methide ((CF₃SO₂)₃C⁻. Non-limiting examplesof suitable ionic liquids includeN-methyl-N-propylpyrrolidinium/bis(fluorosulfonyl) imide and1,2-dimethyl-3-propylimidazolium/bis(trifluoromethanesulfonyl)imide. Insome embodiments, the electrolyte comprises both a room temperatureionic liquid and a lithium salt. In some other embodiments, theelectrolyte comprises a room temperature ionic liquid and does notinclude a lithium salt.

In some embodiments, electrochemical cells may further comprise aseparator interposed between the cathode and anode. In some embodiments,the separator may be proximate to the electrolyte. The separator may bea solid non-conductive or insulative material which separates orinsulates the anode and the cathode from each other preventing shortcircuiting, and which permits the transport of ions between the anodeand the cathode. In some embodiments, the porous separator may bepermeable to the electrolyte.

The pores of the separator may be partially or substantially filled withelectrolyte. Separators may be supplied as porous free standing filmswhich are interleaved with the anodes and the cathodes during thefabrication of cells. Alternatively, the porous separator layer may beapplied directly to the surface of one of the electrodes, for example,as described in PCT Publication No. WO 99/33125 to Carlson et al. and inU.S. Pat. No. 5,194,341 to Bagley et al.

A variety of separator materials are known in the art. Examples ofsuitable solid porous separator materials include, but are not limitedto, polyolefins, such as, for example, polyethylenes (e.g., SETELA™ madeby Tonen Chemical Corp) and polypropylenes, glass fiber filter papers,and ceramic materials. For example, in some embodiments, the separatorcomprises a microporous film (e.g., a microporous polyethylene film).Further examples of separators and separator materials suitable for usein this invention are those comprising a microporous xerogel layer, forexample, a microporous pseudo-boehmite layer, which may be providedeither as a free standing film or by a direct coating application on oneof the electrodes, as described in U.S. Pat. Nos. 6,153,337 and6,306,545 by Carlson et al. of the common assignee. Solid electrolytesand gel electrolytes may also function as a separator in addition totheir electrolyte function.

As noted above, in some embodiments, inventive electrochemical cells canbe under an applied anisotropic force. In some embodiments, theanisotropic force can be applied such that the magnitude of the force issubstantially equal in all directions within a plane defining across-section of the electrochemical cell, but the magnitude of theforces in out-of-plane directions is substantially unequal to themagnitudes of the in-plane forces.

In one set of embodiments, cells described herein are constructed andarranged to apply, during at least one period of time during chargeand/or discharge of the cell, an anisotropic force with a componentnormal to the active surface of the anode. Those of ordinary skill inthe art will understand the meaning of this. In such an arrangement, thecell may be formed as part of a container which applies such a force byvirtue of a “load” applied during or after assembly of the cell, orapplied during use of the cell as a result of expansion and/orcontraction of one or more portions of the cell itself.

The anisotropic force described herein may be applied using any suitablemethod known in the art. In some embodiments, the force may be appliedusing compression springs. For example, referring to FIG. 1,electrochemical cell 100 may be situated in an optional enclosedcontainment structure 170 with one or more compression springs situatedbetween current collector 180 and/or anode 120 and the adjacent wall ofcontainment structure 170 to produce a force with a component in thedirection of arrow 182 to electrodes 110 and 120 and electrolyte 130. Insome embodiments, the force may be applied by situating one or morecompression springs outside the containment structure such that thespring is located between an outside surface of the containmentstructure and another surface (e.g., a tabletop, the inside surface ofanother containment structure, an adjacent cell, etc.). Forces may beapplied using other elements (either inside or outside a containmentstructure) including, but not limited to Belleville washers, machinescrews, pneumatic devices, and/or weights, among others. For example, inone set of embodiments, one or more cells (e.g., a stack of cells) arearranged between two plates (e.g., metal plates). A device (e.g., amachine screw, a spring, etc.) may be used to apply pressure to the endsof the cell or stack via the plates. In the case of a machine screw, forexample, the cells may be compressed between the plates upon rotatingthe screw. As another example, in some embodiments, one or more wedgesmay be displaced between a surface of the cell (or the containmentstructure surrounding the cell) and a fixed surface (e.g., a tabletop,the inside surface of another containment structure, an adjacent cell,etc.). The anisotropic force may be applied by driving the wedge betweenthe cell and the adjacent fixed surface through the application of forceon the wedge (e.g., by turning a machine screw).

The magnitude of the applied force is, in some embodiments, large enoughto enhance the performance of the electrochemical cell. An anode activesurface and the anisotropic force may be, in some instances, togetherselected such that the anisotropic force affects surface morphology ofthe anode active surface to inhibit increase in anode active surfacearea through charge and discharge and wherein, in the absence of theanisotropic force but under otherwise essentially identical conditions,the anode active surface area is increased to a greater extent throughcharge and discharge cycles. “Essentially identical conditions,” in thiscontext, means conditions that are similar or identical other than theapplication and/or magnitude of the force. For example, otherwiseidentical conditions may mean a cell that is identical, but where it isnot constructed (e.g., by brackets or other connections) to apply theanisotropic force on the subject cell.

In some embodiments, an anisotropic force with a component normal to anactive surface of the anode is applied, to an extent effective to causethe anode to have a porosity of less than 20%, 15%, 10%, 5%, or 1%, whenmeasured after having fully cycled the cell 10 times and immediatelyafter the discharge of the tenth cycle.

In some embodiments, an anisotropic force with a component normal to anactive surface of the anode is applied, when the cell is in a fullydischarged state, to an extent effective to cause the remainingnon-lithium metal component to form a region having a sheet resistanceof less than 1000 Ω/sq., 900 Ω/sq., 800 Ω/sq., 700 Ω/sq., 600 Ω/sq., 500Ω/sq., 400 Ω/sq., 300 Ω/sq., 200 Ω/sq., or 100 Ω/sq.

In some embodiments, an anisotropic force with a component normal to anactive surface of the anode is applied, during at least one period oftime during charge and/or discharge of the cell, to an extent effectiveto inhibit an increase in surface area of the anode active surfacerelative to an increase in surface area absent the anisotropic force.The component of the anisotropic force normal to the anode activesurface may, for example, apply a pressure of at least about 4.9, atleast about 9.8, at least about 24.5, at least about 49, at least about78, at least about 98, at least about 117.6, at least about 147, atleast about 175, at least about 200, at least about 225, at least about250, at least about 300, at least about 400, or at least about 500Newtons per square centimeter. In some embodiments, the component of theanisotropic force normal to the anode active surface may, for example,apply a pressure of less than about 500, less than about 400, less thanabout 300, less than about 250, less than about 225, less than about196, less than about 147, less than about 117.6, less than about 98,less than about 49, less than about 24.5, or less than about 9.8 Newtonsper square centimeter. Combinations of the above values are alsopossible. In some cases, the component of the anisotropic force normalto the anode active surface is may apply a pressure of between about 4.9and about 147 Newtons per square centimeter, between about 49 and about117.6 Newtons per square centimeter, between about 68.6 and about 98Newtons per square centimeter, between about 78 and about 108 Newtonsper square centimeter, between about 4.9 and about 250 Newtons persquare centimeter, between about 49 and about 250 Newtons per squarecentimeter, between about 80 and about 250 Newtons per squarecentimeter, between about 90 and about 250 Newtons per squarecentimeter, or between about 100 and about 250 Newtons per squarecentimeter. The force or pressure may, in some embodiments, beexternally-applied to the cell, as described herein. While forces andpressures are generally described herein in units of Newtons and Newtonsper unit area, respectively, forces and pressures can also be expressedin units of kilograms-force (kg_(f)) and kilograms-force per unit area,respectively. One or ordinary skill in the art will be familiar withkilogram-force-based units, and will understand that 1 kilogram-force isequivalent to about 9.8 Newtons.

As described herein, in some embodiments, the surface of an anode can beenhanced during cycling (e.g., for lithium, the development of mossy ora rough surface of lithium may be reduced or eliminated) by applicationof an externally-applied (in some embodiments, uniaxial) pressure. Theexternally-applied pressure may, in some embodiments, be chosen to begreater than the yield stress of a material forming the anode. Forexample, for an anode comprising lithium, the cell may be under anexternally-applied anisotropic force with a component defining apressure of at least about 8 kg_(f)/cm², at least about 9 kg_(f)/cm², atleast about 10 kg_(f)/cm², at least about 20 kg_(f)/cm², at least about30 kg_(f)/cm², at least about 40 kg_(f)/cm², or at least about 50kg_(f)/cm². This is because the yield stress of lithium is around 7-8kg_(f)/cm². Thus, at pressures (e.g., uniaxial pressures) greater thanthis value, mossy Li, or any surface roughness at all, may be reduced orsuppressed. The lithium surface roughness may mimic the surface that ispressing against it. Accordingly, when cycling under at least about 8kg_(f)/cm², at least about 9 kg_(f)/cm², or at least about 10kg_(f)/cm², at least about 20 kg_(f)/cm², at least about 30 kg_(f)/cm²,at least about 40 kg_(f)/cm², or at least about 50 kg_(f)/cm² ofexternally-applied pressure, the lithium surface may become smootherwith cycling when the pressing surface is smooth. As described herein,the pressing surface may be modified by choosing the appropriatematerial(s) positioned between the anode and the cathode.

In some cases, one or more forces applied to the cell have a componentthat is not normal to an active surface of an anode. For example, inFIG. 1, force 184 is not normal to active surface 185 of electrode 110.In one set of embodiments, the sum of the components of all appliedanisotropic forces in a direction normal to the anode active surface islarger than any sum of components in a direction that is non-normal tothe anode active surface. In some embodiments, the sum of the componentsof all applied anisotropic forces in a direction normal to the anodeactive surface is at least about 5%, at least about 10%, at least about20%, at least about 35%, at least about 50%, at least about 75%, atleast about 90%, at least about 95%, at least about 99%, or at leastabout 99.9% larger than any sum of components in a direction that isparallel to the anode active surface.

In some cases, cells may be pre-compressed before they are inserted intocontainment structures, and, upon being inserted to the containmentstructure, they may expand to produce a net force on the cell. Such anarrangement may be advantageous, for example, if the cell is capable ofwithstanding relatively high variations in pressure. In suchembodiments, the containment structures may have a relatively highstrength (e.g., at least about 100 MPa, at least about 200 MPa, at leastabout 500 MPa, or at least about 1 GPa). In addition, the containmentstructure may have a relatively high elastic modulus (e.g., at leastabout 10 GPa, at least about 25 GPa, at least about 50 GPa, or at leastabout 100 GPa). The containment structure may comprise, for example,aluminum, titanium, or any other suitable material.

The following applications are incorporated herein by reference, intheir entirety, for all purposes: U.S. Patent Publication No. US2007/0221265, published on Sep. 27, 2007, filed as application Ser. No.11/400,781 on Apr. 6, 2006, and entitled “Rechargeable Lithium/Water,Lithium/Air Batteries”; U.S. Patent Publication No. US 2009/0035646,published on Feb. 5, 2009, filed as application Ser. No. 11/888,339 onJul. 31, 2007, and entitled “Swelling Inhibition in Batteries”; U.S.Patent Publication No. US 2010/0129699, published on May 17, 2010, filedas application Ser. No. 12/312,674 on Feb. 2, 2010, patented as U.S.Pat. No. 8,617,748 on Dec. 31, 2013, and entitled “Separation ofElectrolytes”; U.S. Patent Publication No. US 2010/0291442, published onNov. 18, 2010, filed as application Ser. No. 12/682,011 on Jul. 30,2010, patented as U.S. Pat. No. 8,871,387 on Oct. 28, 2014, and entitled“Primer for Battery Electrode”; U.S. Patent Publication No. US2009/0200986, published on Aug. 31, 2009, filed as application Ser. No.12/069,335 on Feb. 8, 2008, patented as U.S. Pat. No. 8,264,205 on Sep.11, 2012, and entitled “Circuit for Charge and/or Discharge Protectionin an Energy-Storage Device”; U.S. Patent Publication No. US2007/0224502, published on Sep. 27, 2007, filed as application Ser. No.11/400,025 on Apr. 6, 2006, patented as U.S. Pat. No. 7,771,870 on Aug.10, 2010, and entitled “Electrode Protection in Both Aqueous andNon-Aqueous Electrochemical cells, Including Rechargeable LithiumBatteries”; U.S. Patent Publication No. US 2008/0318128, published onDec. 25, 2008, filed as application Ser. No. 11/821,576 on Jun. 22,2007, and entitled “Lithium Alloy/Sulfur Batteries”; U.S. PatentPublication No. US 2002/0055040, published on May 9, 2002, filed asapplication Ser. No. 09/795,915 on Feb. 27, 2001, patented as U.S. Pat.No. 7,939,198 on May 10, 2011, and entitled “Novel Composite Cathodes,Electrochemical Cells Comprising Novel Composite Cathodes, and Processesfor Fabricating Same”; U.S. Patent Publication No. US 2006/0238203,published on Oct. 26, 2006, filed as application Ser. No. 11/111,262 onApr. 20, 2005, patented as U.S. Pat. No. 7,688,075 on Mar. 30, 2010, andentitled “Lithium Sulfur Rechargeable Battery Fuel Gauge Systems andMethods”; U.S. Patent Publication No. US 2008/0187663, published on Aug.7, 2008, filed as application Ser. No. 11/728,197 on Mar. 23, 2007,patented as U.S. Pat. No. 8,084,102 on Dec. 27, 2011, and entitled“Methods for Co-Flash Evaporation of Polymerizable Monomers andNon-Polymerizable Carrier Solvent/Salt Mixtures/Solutions”; U.S. PatentPublication No. US 2011/0006738, published on Jan. 13, 2011, filed asapplication Ser. No. 12/679,371 on Sep. 23, 2010, and entitled“Electrolyte Additives for Lithium Batteries and Related Methods”; U.S.Patent Publication No. US 2011/0008531, published on Jan. 13, 2011,filed as application Ser. No. 12/811,576 on Sep. 23, 2010, patented asU.S. Pat. No. 9,034,421 on May 19, 2015, and entitled “Methods ofForming Electrodes Comprising Sulfur and Porous Material ComprisingCarbon”; U.S. Patent Publication No. US 2010/0035128, published on Feb.11, 2010, filed as application Ser. No. 12/535,328 on Aug. 4, 2009,patented as U.S. Pat. No. 9,105,938 on Aug. 11, 2015, and entitled“Application of Force in Electrochemical Cells”; U.S. Patent PublicationNo. US 2011/0165471, published on Jul. 15, 2011, filed as applicationSer. No. 12/180,379 on Jul. 25, 2008, and entitled “Protection of Anodesfor Electrochemical Cells”; U.S. Patent Publication No. US 2006/0222954,published on Oct. 5, 2006, filed as application Ser. No. 11/452,445 onJun. 13, 2006, patented as U.S. Pat. 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No. 9,077,041 on Jul.7, 2015, and entitled “Electrode Structure for Electrochemical Cell”;U.S. Patent Publication No. US 2013/0252103, published on Sep. 26, 2013,filed as application Ser. No. 13/789,783 on Mar. 8, 2013, patented asU.S. Pat. No. 9,214,678 on Dec. 15, 2015, and entitled “Porous SupportStructures, Electrodes Containing Same, and Associated Methods”; U.S.Patent Publication No. US 2013/0095380, published on Apr. 18, 2013,filed as application Ser. No. 13/644,933 on Oct. 4, 2012, patented asU.S. Pat. No. 8.936,870 on Jan. 20, 2015, and entitled “ElectrodeStructure and Method for Making the Same”; U.S. Patent Publication No.US 2014/0123477, published on May 8, 2014, filed as application Ser. No.14/069,698 on Nov. 1, 2013, patented as U.S. Pat. No. 9,005,311 on Apr.14, 2015, and entitled “Electrode Active Surface Pretreatment”; U.S.Patent Publication No. US 2014/0193723, published on Jul. 10, 2014,filed as application Ser. No. 14/150,156 on Jan. 8, 2014, patented asU.S. Pat. No. 9,559,348 on Jan. 31, 2017, and entitled “ConductivityControl in Electrochemical Cells”; U.S. Patent Publication No. US2014/0255780, published on Sep. 11, 2014, filed as application Ser. No.14/197,782 on Mar. 5, 2014, patented as U.S. Pat. No. 9,490,478 on Nov.6, 2016, and entitled “Electrochemical Cells Comprising FibrilMaterials”; U.S. Patent Publication No. US 2014/0272594, published onSep. 18, 2014, filed as application Ser. No. 13/833,377 on Mar. 15,2013, and entitled “Protective Structures for Electrodes”; U.S. PatentPublication No. US 2014/0272597, published on Sep. 18, 2014, filed asapplication Ser. No. 14/209,274 on Mar. 13, 2014, and entitled“Protected Electrode Structures and Methods”; U.S. Patent PublicationNo. US 2014/0193713, published on Jul. 10, 2014, filed as ApplicationNo. 14/150,196 on Jan. 8, 2014, patented as U.S. Pat. No. 9,531,009 onDec. 27, 2016, and entitled “Passivation of Electrodes inElectrochemical Cells”; U.S. Patent Publication No. US 2014/0272565,published on Sep. 18, 2014, filed as application Ser. No. 14/209,396 onMar. 13, 2014, and entitled “Protected Electrode Structures”; U.S.Patent Publication No. US 2015/0010804, published on Jan. 8, 2015, filedas application Ser. No. 14/323,269 on Jul. 3, 2014, and entitled“Ceramic/Polymer Matrix for Electrode Protection in ElectrochemicalCells, Including Rechargeable Lithium Batteries”; U.S. PatentPublication No. US 2015/044517, published on Feb. 12, 2015, filed asapplication Ser. No. 14/455,230 on Aug. 8, 2014, and entitled“Self-Healing Electrode Protection in Electrochemical Cells”; U.S.Patent Publication No. US 2015/0236322, published on Aug. 20, 2015,filed as application Ser. No. 14/184,037 on Feb. 19, 2014, and entitled“Electrode Protection Using Electrolyte-Inhibiting Ion Conductor”; andU.S. Patent Publication No. US 2016/0072132, published on Mar. 10, 2016,filed as application Sere. No. 14/848,659 on Sep. 9, 2015, and entitled“Protective Layers in Lithium-Ion Electrochemical Cells and AssociatedElectrodes and Methods”.

U.S. Provisional Application No. 62/517,409, filed Jun. 9, 2017, andentitled “In Situ Current Collector” is incorporated herein by referencein its entirety for all purposes.

EXAMPLES

The following examples are intended to illustrate certain embodiments ofthe present invention, but do not exemplify the full scope of theinvention.

In the following examples and comparative examples, the cells wereprepared by the following methods. For the examples incorporatingnon-limiting embodiments of the disclosed invention, an anode was madeof a 2 mil Li/Mg solid solution. For the comparative examples an anodewas made of a conventional 2 mil Li foil. The cathodes used in both theexamples and comparative examples were lithium cobalt oxide (LCO)cathodes. The porous separator used in both the examples and comparativeexamples was 25 μm polyolefin (Celgard 2325). The above components wereassembled to form electrochemical cells in a stacked layer structure ofcathode/separator/anode/separator/cathode, with an active cathodematerial loading of 21 mg/cm²/per side. The total active surface area ofeach cell was 16.6 cm². After sealing the cell components in a foilpouch, 0.3 mL of LP30 electrolyte from BASF [1M lithiumhexafluorophosphate (LiPF₆) in a 1:1 weight ratio mixture of dimethylcarbonate (DMC) and ethylene carbonate (EC)] was added. The cell packagewas then vacuum sealed.

These cells were allowed to soak in the electrolyte for 24 hoursunrestrained and then 10 kg/cm² pressure was applied. All the cells werecycled under such pressure. Charge and discharge cycling was performedat standard C/8 (12.5 mA) and C/5 rate (20mA), respectively, with acharge cutoff voltage of 4.2 V or 4.3 V followed by taper at 4.2 V or4.3 V to 1 mA, and discharge cutoff at 2.5 V. Cell charge/dischargecycling was repeated until cells in a charged state reached only an 80%capacity of their original capacity. The number of cycles it took toreach this reduced-capacity state was observed.

Example 1

A 2 mil thick anode comprising a Li/Mg solid solution, according to anembodiment of the invention, was incorporated in an electrochemical cellmanufactured and operated according to the conditions described above.The charge voltage cut-off was 4.2 V.

Example 2

A 2 mil thick anode comprising a Li/Mg solid solution, according to anembodiment of the invention, was incorporated in an electrochemical cellmanufactured and operated according to the conditions described above.The charge voltage cut-off was 4.3 V.

Comparative Example 1

In the first comparative example, a conventional 2 Mil Li foil was usedas the anode in an electrochemical cell manufactured and operatedaccording to the conditions described above. The charge voltage cut-offwas 4.2 V.

Comparative Example 2

In the second comparative example a conventional 2 Mil Li foil was usedas the anode in an electrochemical cell manufactured and operatedaccording to the conditions described above. The charge voltage cut-offwas 4.3 V.

RESULTS

As shown in Table 1, the use of Li/Mg solid solution as anode, example 1and 2 showed significant improvement in cycle life over that comparativeexamples.

TABLE 1 Cycle performances of examples and comparative examples: #Cyclesto 80% Capacity Example 1 72 Example 2 76 Comparative Example 1 29Comparative Example 2 28

As shown in Table 1, the electrochemical cells of Examples 1 and 2,which incorporated an anode comprising a lithium magnesium solidsolution, were able to be cycled 72 and 76 times, respectively, beforetheir capacity in a discharged state was reduced to 80% of theiroriginal capacity. In contrast, the electrochemical cells of ComparativeExamples 1 and 2 were reduced to 80% of their original capacity after 29and 28 cycles, respectively. These trials indicate an improvedperformance resulting from the use of the disclosed solid solutionanodes.

Furthermore, the end-of-life cells were opened to examine the integrityof Li and Li/Mg solid solution. FIG. 3A shows an optical image of theelectrochemical cell of comparative example 1, in which a conventionallithium anode was employed. It can be clearly observed that the lithiumis flaky and loss of connections in many localized areas. FIG. 3B showsan optical image of the electrochemical cell of Example 1, in which ananode comprising a Li/Mg solid solution, according to an embodiment ofthe invention, was incorporated. FIG. 3B shows that the Li/Mg solidsolution remained as an intact sheet.

While several embodiments of the present invention have been describedand illustrated herein, those of ordinary skill in the art will readilyenvision a variety of other means and/or structures for performing thefunctions and/or obtaining the results and/or one or more of theadvantages described herein, and each of such variations and/ormodifications is deemed to be within the scope of the present invention.More generally, those skilled in the art will readily appreciate thatall parameters, dimensions, materials, and configurations describedherein are meant to be exemplary and that the actual parameters,dimensions, materials, and/or configurations will depend upon thespecific application or applications for which the teachings of thepresent invention is/are used. Those skilled in the art will recognize,or be able to ascertain using no more than routine experimentation, manyequivalents to the specific embodiments of the invention describedherein. It is, therefore, to be understood that the foregoingembodiments are presented by way of example only and that, within thescope of the appended claims and equivalents thereto, the invention maybe practiced otherwise than as specifically described and claimed. Thepresent invention is directed to each individual feature, system,article, material, and/or method described herein. In addition, anycombination of two or more such features, systems, articles, materials,and/or methods, if such features, systems, articles, materials, and/ormethods are not mutually inconsistent, is included within the scope ofthe present invention.

For the purpose of clarity, it should be understood that when referenceis made to the electrochemical cell or a component of the cell (e.g., ananode) having a certain characteristic (such as a certain porosity orsheet resistance) when measured at a specific point in the life cycle ofthe cell (e.g. immediately after the discharge of the tenth cycle), sucha reference constitutes a screening test for measuring a characteristicof the cell (or other claimed apparatus). Screening tests within a claimshould be interpreted such that an apparatus (e.g., electrochemicalcell) should be understood to meet the limitation recited in thescreening test, where the apparatus would possess the recitedcharacteristic (e.g., porosity, sheet resistance) upon being subjectedto the screening test, even if the apparatus has not yet been subjectedto the screening test, or otherwise has not reached the described pointin the life cycle at which the test is to take place.

The indefinite articles “a” and “an,” as used herein in thespecification and in the claims, unless clearly indicated to thecontrary, should be understood to mean “at least one.”

The phrase “and/or,” as used herein in the specification and in theclaims, should be understood to mean “either or both” of the elements soconjoined, i.e., elements that are conjunctively present in some casesand disjunctively present in other cases. Other elements may optionallybe present other than the elements specifically identified by the“and/or” clause, whether related or unrelated to those elementsspecifically identified unless clearly indicated to the contrary. Thus,as a non-limiting example, a reference to “A and/or B,” when used inconjunction with open-ended language such as “comprising” can refer, inone embodiment, to A without B (optionally including elements other thanB); in another embodiment, to B without A (optionally including elementsother than A); in yet another embodiment, to both A and B (optionallyincluding other elements); etc.

As used herein in the specification and in the claims, “or” should beunderstood to have the same meaning as “and/or” as defined above. Forexample, when separating items in a list, “or” or “and/or” shall beinterpreted as being inclusive, i.e., the inclusion of at least one, butalso including more than one, of a number or list of elements, and,optionally, additional unlisted items. Only terms clearly indicated tothe contrary, such as “only one of” or “exactly one of,” or, when usedin the claims, “consisting of,” will refer to the inclusion of exactlyone element of a number or list of elements. In general, the term “or”as used herein shall only be interpreted as indicating exclusivealternatives (i.e. “one or the other but not both”) when preceded byterms of exclusivity, such as “either,” “one of,” “only one of,” or“exactly one of.” “Consisting essentially of,” when used in the claims,shall have its ordinary meaning as used in the field of patent law.

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood to mean at least one element selected from any one or more ofthe elements in the list of elements, but not necessarily including atleast one of each and every element specifically listed within the listof elements and not excluding any combinations of elements in the listof elements. This definition also allows that elements may optionally bepresent other than the elements specifically identified within the listof elements to which the phrase “at least one” refers, whether relatedor unrelated to those elements specifically identified. Thus, as anon-limiting example, “at least one of A and B” (or, equivalently, “atleast one of A or B,” or, equivalently “at least one of A and/or B”) canrefer, in one embodiment, to at least one, optionally including morethan one, A, with no B present (and optionally including elements otherthan B); in another embodiment, to at least one, optionally includingmore than one, B, with no A present (and optionally including elementsother than A); in yet another embodiment, to at least one, optionallyincluding more than one, A, and at least one, optionally including morethan one, B (and optionally including other elements); etc.

In the claims, as well as in the specification above, all transitionalphrases such as “comprising,” “including,” “carrying,” “having,”“containing,” “involving,” “holding,” and the like are to be understoodto be open-ended, i.e., to mean including but not limited to. Only thetransitional phrases “consisting of” and “consisting essentially of”shall be closed or semi-closed transitional phrases, respectively, asset forth in the United States Patent Office Manual of Patent ExaminingProcedures, Section 2111.03.

What is claimed is: 1-76. (canceled)
 77. An electrochemical cellcomprising: a cathode; an anode comprising a solid solution of lithiumand at least one non-lithium metal, the anode having an active surface;and an electrolyte in electrochemical communication with the cathode andthe anode; wherein: the electrochemical cell is under an appliedanisotropic force having a force component normal to the active surfaceof the anode; and the anisotropic force and the electrochemical cell areconfigured such that, when the electrochemical cell is fully cycled 10times, the anode has a porosity of less than 20% immediately after thedischarge of the tenth cycle, and 75 wt % or less of the amount oflithium present in the anode in its initial fully-charged state remainsin the anode immediately after the discharge of the tenth cycle.
 78. Theelectrochemical cell of claim 77, wherein the at least one non-lithiummetal is selected from the group consisting of magnesium, zinc, lead,tin, platinum, gold, aluminum, cadmium, silver, mercury, andcombinations thereof.
 79. The electrochemical cell of claim 77, whereinthe at least one non-lithium metal is selected from the group consistingof magnesium, zinc, lead, platinum, gold, cadmium, silver, mercury, andcombinations thereof.
 80. The electrochemical cell of claim 77, whereinthe at least one non-lithium metal excludes the group consisting ofsilicon, germanium, tin, antimony, bismuth, and aluminum.
 81. Theelectrochemical cell of claim 77, wherein the at least one non-lithiummetal comprises magnesium.
 82. The electrochemical cell of claim 77,wherein the at least one non-lithium metal in the anode is at least 0.1wt % and equal to or less than 25 wt % of the combined weight of lithiumand non-lithium metal in the anode during a fully charged state.
 83. Theelectrochemical cell of claim 77, wherein, when the electrochemical cellis fully cycled 10 times, the anode has a sheet resistance of less than1000 Ω/sq. immediately after the discharge of the tenth cycle.
 84. Theelectrochemical cell of claim 77, wherein, when the electrochemical cellis fully cycled 10 times, 60 wt % or less of the amount of lithiumpresent in the anode in its initial fully-charged state remains in theanode immediately after the discharge of the tenth cycle.
 85. Theelectrochemical cell of claim 77, wherein the anisotropic force and theelectrochemical cell are configured such that, when the electrochemicalcell is fully cycled 50 times, the anode has a porosity of less than 20%immediately after the discharge of the 50^(th) cycle, and 75 wt % orless of the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the 50^(th) cycle.
 86. An electrochemical cell comprising: a cathode;an anode comprising a solid solution of lithium and at least onenon-lithium metal, the anode having an active surface; and anelectrolyte in electrochemical communication with the cathode and theanode; wherein: the electrochemical cell is under an applied anisotropicforce having a force component normal to the active surface of theanode; and the at least one non-lithium metal is present at a sufficientvolume such that, when the electrochemical cell is fully cycled 10times, the anode has a porosity of less than 20% immediately after thedischarge of the tenth cycle, and 75 wt % or less of the amount oflithium present in the anode in its initial fully-charged state remainsin the anode immediately after the discharge of the tenth cycle.
 87. Theelectrochemical cell of claim 86, wherein the at least one non-lithiummetal is selected from the group consisting of magnesium, zinc, lead,tin, platinum, gold, aluminum, cadmium, silver, mercury, andcombinations thereof.
 88. The electrochemical cell of claim 86, whereinthe at least one non-lithium metal is selected from the group consistingof magnesium, zinc, lead, platinum, gold, cadmium, silver, mercury, andcombinations thereof.
 89. The electrochemical cell of claim 86, whereinthe at least one non-lithium metal excludes the group consisting ofsilicon, germanium, tin, antimony, bismuth, and aluminum.
 90. Theelectrochemical cell of claim 86, wherein the at least one non-lithiummetal comprises magnesium.
 91. The electrochemical cell of claim 86,wherein the at least one non-lithium metal in the anode is at least 0.1wt % and equal to or less than 25 wt % of the combined weight of lithiumand non-lithium metal in the anode during a fully charged state.
 92. Theelectrochemical cell of claim 86, wherein, when the electrochemical cellis fully cycled 10 times, the anode has a sheet resistance of less than1000 Ω/sq. immediately after the discharge of the tenth cycle.
 93. Theelectrochemical cell of claim 86, wherein, when the electrochemical cellis fully cycled 10 times, 60 wt % or less of the amount of lithiumpresent in the anode in its initial fully-charged state remains in theanode immediately after the discharge of the tenth cycle.
 94. Theelectrochemical cell of claim 86, wherein the at least one non-lithiummetal is present at a sufficient volume such that, when theelectrochemical cell is fully cycled 50 times, the anode has a porosityof less than 20% immediately after the discharge of the 50^(th) cycle,and 75 wt % or less of the amount of lithium present in the anode in itsinitial fully-charged state remains in the anode immediately after thedischarge of the 50^(th) cycle.
 95. An electrochemical cell comprising:a cathode; an anode comprising a solid solution of lithium and at leastone non-lithium metal, the anode having an active surface; and anelectrolyte in electrochemical communication with the cathode and theanode; wherein: the electrochemical cell is under an applied anisotropicforce having a force component normal to the active surface of theanode; and the anisotropic force and the electrochemical cell areconfigured such that, when the electrochemical cell is fully cycled 10times, the anode has a sheet resistance of less than 1000 Ω/sq.immediately after the discharge of the tenth cycle, and 75 wt % or lessof the amount of lithium present in the anode in its initialfully-charged state remains in the anode immediately after the dischargeof the tenth cycle.
 96. The electrochemical cell of claim 95, whereinthe at least one non-lithium metal is selected from the group consistingof magnesium, zinc, lead, tin, platinum, gold, aluminum, cadmium,silver, mercury, and combinations thereof.
 97. The electrochemical cellof claim 95, wherein the at least one non-lithium metal is selected fromthe group consisting of magnesium, zinc, lead, platinum, gold, cadmium,silver, mercury, and combinations thereof.
 98. The electrochemical cellof claim 95, wherein the at least one non-lithium metal excludes thegroup consisting of silicon, germanium, tin, antimony, bismuth, andaluminum.
 99. The electrochemical cell of claim 95, wherein the at leastone non-lithium metal comprises magnesium.
 100. The electrochemical cellof claim 95, wherein the at least one non-lithium metal in the anode isat least 0.1 wt % and equal to or less than 25 wt % of the combinedweight of lithium and non-lithium metal in the anode during a fullycharged state.
 101. The electrochemical cell of claim 95, wherein, whenthe electrochemical cell is fully cycled 10 times, the anode has aporosity of less than 20% immediately after the discharge of the tenthcycle.
 102. The electrochemical cell of claim 95, wherein, when theelectrochemical cell is fully cycled 10 times, 60 wt % or less of theamount of lithium present in the anode in its initial fully-chargedstate remains in the anode immediately after the discharge of the tenthcycle.
 103. The electrochemical cell of claim 95, wherein theanisotropic force and the electrochemical cell are configured such that,when the electrochemical cell is fully cycled 50 times, the anode has asheet resistance of less than 1000 Ω/sq. immediately after the dischargeof the 50^(th) cycle, and 75 wt % or less of the amount of lithiumpresent in the anode in its initial fully-charged state remains in theanode immediately after the discharge of the 50^(th) cycle.
 104. Anelectrochemical cell comprising: a cathode; an anode comprising a solidsolution of lithium and at least one non-lithium metal, the anode havingan active surface; and an electrolyte in electrochemical communicationwith the cathode and the anode; wherein: the electrochemical cell isunder an applied anisotropic force having a force component normal tothe active surface of the anode; and the at least one non-lithium metalis present at a sufficient volume such that, when the electrochemicalcell is fully cycled 10 times, the at least one non-lithium metal formsa region having a sheet resistance of less than 1000 Ω/sq. immediatelyafter the discharge of the tenth cycle, and 75 wt % or less of theamount of lithium present in the anode in its initial fully-chargedstate remains in the anode immediately after the discharge of the tenthcycle.
 105. The electrochemical cell of claim 104, wherein the at leastone non-lithium metal is selected from the group consisting ofmagnesium, zinc, lead, tin, platinum, gold, aluminum, cadmium, silver,mercury, and combinations thereof.
 106. The electrochemical cell ofclaim 104, wherein the at least one non-lithium metal is selected fromthe group consisting of magnesium, zinc, lead, platinum, gold, cadmium,silver, mercury, and combinations thereof.
 107. The electrochemical cellof claim 104, wherein the at least one non-lithium metal excludes thegroup consisting of silicon, germanium, tin, antimony, bismuth, andaluminum.
 108. The electrochemical cell of claim 104, wherein the atleast one non-lithium metal comprises magnesium.
 109. Theelectrochemical cell of claim 104, wherein the at least one non-lithiummetal in the anode is at least 0.1 wt % and equal to or less than 25 wt% of the combined weight of lithium and non-lithium metal in the anodeduring a fully charged state.
 110. The electrochemical cell of claim104, wherein, when the electrochemical cell is fully cycled 10 times,the anode has a porosity of less than 20% immediately after thedischarge of the tenth cycle.
 111. The electrochemical cell of claim104, wherein, when the electrochemical cell is fully cycled 10 times, 60wt % or less of the amount of lithium present in the anode in itsinitial fully-charged state remains in the anode immediately after thedischarge of the tenth cycle.
 112. The electrochemical cell of claim104, wherein the at least one non-lithium metal is present at asufficient volume such that, when the electrochemical cell is fullycycled 50 times, the at least one non-lithium metal forms a regionhaving a sheet resistance of less than 1000 Ω/sq. immediately after thedischarge of the 50^(th) cycle, and 75 wt % or less of the amount oflithium present in the anode in its initial fully-charged state remainsin the anode immediately after the discharge of the 50^(th) cycle.